U.S. patent number 4,465,889 [Application Number 06/394,795] was granted by the patent office on 1984-08-14 for catalytic conversion of methanol, dimethyl ether and mixtures thereof to a hydrocarbon product rich in iso-c.sub.4 compounds and new catalysts therefor.
This patent grant is currently assigned to Summit Gas Systems Pte. Ltd.. Invention is credited to Rayford G. Anthony, P. E. Thomas.
United States Patent |
4,465,889 |
Anthony , et al. |
August 14, 1984 |
Catalytic conversion of methanol, dimethyl ether and mixtures
thereof to a hydrocarbon product rich in iso-C.sub.4 compounds and
new catalysts therefor
Abstract
Methanol, dimethyl ether or a mixture thereof is converted to a
hydrocarbon product rich in iso-C.sub.4 compounds by contact with a
catalyst comprised of crystalline silica having molecular sieve
properties or a crystalline solid with molecular sieve properties
which has been impregnated with thorium oxide, zirconium oxide,
titanium oxide or a combination thereof.
Inventors: |
Anthony; Rayford G. (Bryan,
TX), Thomas; P. E. (Thottakad, IN) |
Assignee: |
Summit Gas Systems Pte. Ltd.
(Jurong, SG)
|
Family
ID: |
23560451 |
Appl.
No.: |
06/394,795 |
Filed: |
July 2, 1982 |
Current U.S.
Class: |
585/640; 502/236;
502/239; 502/240; 502/242; 502/71; 502/77; 585/408; 585/469;
585/733 |
Current CPC
Class: |
B01J
29/035 (20130101); C07C 1/20 (20130101); Y02P
20/52 (20151101); C07C 2521/08 (20130101) |
Current International
Class: |
B01J
29/00 (20060101); B01J 29/035 (20060101); C07C
1/20 (20060101); C07C 1/00 (20060101); C07C
001/22 () |
Field of
Search: |
;585/408,469,640,733,639
;252/455Z,449 ;502/63,236,239,240,242 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Anderson et al., J. Catalysis, 58, 114, (1979). .
Olson et al., J. Catalysis, 61, 390, (1980). .
Wu et al., J. Phys. Chem., 83, 2777, (1979). .
Rao et al., ACS, Div. Fuel Chem., (ACFPA), 25(2), 119,
(1979)..
|
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Pal; A.
Attorney, Agent or Firm: Burns; Robert E. Lobato; Emmanuel
J. Adams; Bruce L.
Claims
What we desire to claim and protect by Letters Patent is:
1. A process for converting methanol, dimethyl ether or a mixture
thereof to a hydrocarbon product rich in iso-C.sub.4 compounds
comprising
contacting methanol, dimethyl ether or a mixture thereof with a
catalyst consisting essentially of silicalite impregnated with an
oxide selected from the group consisting of thorium oxide,
zirconium oxide, titanium oxide, and a combination thereof, at a
temperature of about 300.degree. C. to 550.degree. C., whereby the
gaseous product contains about 20% to 50% by weight of iso-C.sub.4
compounds.
2. The process according to claim 1 in which methanol is contacted
with said catalyst.
3. The process according to claim 1 in which said methanol,
dimethyl ether or mixture thereof is combined with water.
4. The process according to claim 1 in which methanol, dimethyl
ether or mixture thereof combined with up to 80% by weight of water
is contacted with said catalyst.
5. The process according to claim 1 in which a mixture containing
methanol in an amount of about 60 to 30% by weight and water in an
amount of about 40 to 70% by weight is contacted with said
catalyst.
6. The process according to claim 1 in which an equilibrium mixture
of methanol, dimethyl ether and water is contacted with said
catalyst.
7. The process according to claim 1 in which C.sub.2, C.sub.3 and
aromatic hydrocarbons are produced during the conversion of
methanol, dimethyl ether or a mixture thereof to said hydrocarbon
product and in which water is added to said feed to increase the
production of C.sub.2 and C.sub.3 hydrocarbons, to increase the
olefinic content of the C.sub.2 and C.sub.3 hydrocarbons and to
decrease the production of said aromatic hydrocarbons.
8. The process according to claim 1 in which said conversion is
carried out at a temperature of about 330.degree. to 455.degree.
C.
9. The process according to claim 1, in which said oxide is thorium
oxide.
10. The process according to claim 1, in which said oxide is
zirconium oxide.
11. The process according to claim 1, in which said oxide is
titanium oxide.
12. The process according to claim 1, in which said crystalline
solid has been impregnated with a mixture of said oxides.
13. The process according to claim 1, wherein said catalyst
contains 0.5 to 30% by weight of said oxide.
14. The process according to claim 1, in which said catalyst
contains about 2 to 15 parts by weight of said oxide.
15. The process according to claim 1 in which the gaseous product
contains at least about 30% by weight of the iso-C.sub.4
compounds.
16. A catalyst useful for converting methanol, dimethyl ether and a
mixture thereof to a hydrocarbon product rich in iso-C.sub.4
compounds consisting essentially of silicalite and from about 0.5
to 30% of oxide selected from the group consisting of thorium
oxide, zirconium oxide, titanium oxide or a combination thereof
impregnated therein.
17. The catalyst according to claim 16 which contains about 2 to 15
parts by weight of said oxide.
18. The catalyst according to claim 16 in which said oxide is
thorium oxide.
19. The catalyst according to claim 16 in which said oxide is
zirconium oxide.
20. The catalyst according to claim 16 in which said oxide is
titanium oxide.
21. The catalyst according to claim 18 in which a combination of
said oxides is impregnated in said silicalite.
Description
BACKGROUND OF THE INVENTION
This invention relates to a method for converting methanol and/or
dimethyl ether to a hydrocarbon product, particularly a hydrocarbon
product rich in isobutane and isobutene. The invention is also
concerned with new catalysts, by means of which methanol and/or
dimethyl ether is converted to a hydrocarbon product rich in
iso-C.sub.4 compounds.
Isobutene or isobutylene and isobutane are important starting
materials for the preparation of a variety of commercially
important products, including maleic anhydride-isobutylene
copolymer, 2,5-dimethylhexadiene, which is a key intermediate in
the manufacturer of pyrethrin insecticides, butyl rubber,
polybutenes, methyl methacrylate, alkylate, which is a blending
component for high octane gasoline and methyl t-butyl ether, which
is also a blending component for high octane gasoline.
At present, isobutylene is obtained generally from the cracking of
liquid petroleum or from naturally occurring field butanes.
However, the demand for isobutylene far exceeds the supply, and
this demand is increasing.
The synthesis of branched chain hydrocarbons from synthesis or
water gas, i.e., a mixture of carbon monoxide and hydrogen, has
been investigated at the Kaiser Wilhelm Institute For Coal
Research, Germany; according to a translation of a report by
Pichler and Ziesecke, Bureau Of Mines Bulletin, 488, U.S.
Government Printing Office, Washington, D.C. 1950, water gas has
been converted under high pressure and elevated temperature to a
hydrocarbon product containing isobutylene by means of a variety of
catalysts, including catalysts composed principally of an oxide of
thorium, aluminum, tungsten, chromium, titanium, zirconium,
uranium, zinc, manganese or cerium and mixtures of thorium oxide
with alumina, zinc oxide, chromium oxide, iron and copper.
While the work of Pichler et al. shows that water gas can be
converted into a hydrocarbon product containing iso-C.sub.4
hydrocarbons, the Pichler et al. process has serious shortcomings
which have prevented its commercial use. In particular, the
conversion is carried out at very high pressure, i.e., from 30 to
1,000 atms.; the higher the pressure, the better the conversion;
however, high pressure equipment is very expensive. Further,
thorium oxide is also costly and the concentration of thorium oxide
in the Pichler et al. catalyst is high, i.e., about 71-100 percent
by weight.
More recently, crystalline aluminosilicate zeolites or molecular
sieves have been disclosed and shown to be useful for catalyzing a
variety of reactions. For example, according to U.S. Pat. No.
3,036,134, alcohols may be converted to ethers, by means of a
crystalline aluminosilicate of the formula:
wherein M is a metal and n its valence, X varies from about 1.35 to
3 and the average value for Y is between 4 and 8.
The dehydration of a normal alcohol to an olefin having a
corresponding structure by means of such a synthetic zeolite or
molecular sieve is disclosed in U.S. Pat. No. 3,529,033.
According to U.S. Pat. No. 4,079,096, a catalyst of crystalline
aluminosilicate zeolite is also useful to convert methanol and/or
dimethyl ether to a hydrocarbon product rich in ethylene and
propylene. Reactions of polar organic compounds through the use of
zeolite catalysts are disclosed in U.S. Pat. No. 3,728,408; the
production of aromatic compounds from liquid hydrocarbons using a
crystalline aluminosilicate catalyst is taught as U.S. Pat. Nos.
3,756,942 and 3,760,024, and the aromatization of alcohols, ethers
and carbonyl-containing compounds by means of a crystalline
aluminosilicate zeolite in U.S. Pat. No. 3,894,104. The use of a
crystalline aluminosilicate zeolite catalyst to convert lower
aliphatic alcohols, carbonyls, ethers and the like to a hydrocarbon
product rich in compounds containing 5 or more carbon atoms has
been disclosed in U.S. Pat. No. 3,894,103, while the conversion of
compound of formula CH.sub.3 X, wherein X is a hydroxyl, alkoxy,
alkylthio, amino, alkylamine dialkylamine, halo or cyano group to
aromatic compounds is taught in U.S. Pat. No. 3,894,105, and the
conversion of methanol and/or dimethyl ether to a hydrocarbon
product rich in ethylene and propylene is taught in U.S. Pat. No.
4,062,905.
German Pat. Nos. 2,827,385 and 2,755,229 also concern the
conversion of methanol and/or dimethyl ether by means of a zeolite
catalyst to a hydrocarbon product rich in ethylene and
propylene.
Recently, a crystalline silica composition of uniform pore
diameter, which exhibits molecular sieve and hydrophobic
organophilic properties, but not ion exchange properties has been
disclosed by Gross et al. in U.S. Pat. No. 4,061,724, which is
incorporated herein by reference. According to Gross et al., this
silica composition, which is referred to as silicalite is
substantially free of alumina except for incidental impurities and
the crystals thereof are orthorhombic. Silicalite has also been
characterized as a silica polymorph, which after calcination in air
at 600.degree. C. for 1 hour, has a mean refractive index of 1.39
and a specific gravity at 25.degree. C. of 1.70. Due to its uniform
pore structure, silicalite is disclosed as being useful to separate
p-xylene from o-xylene and as being useful for selectively
absorbing organic materials from water as a result of its
hydrophobic/organophilic properties.
SUMMARY OF THE INVENTION
An object of the present invention is the provision of a process
for converting methanol and/or dimethyl ether to hydrocarbons rich
in isobutane and isobutene.
Another object of the present invention is the provision of a
process for obtaining isobutene and isobutane from methanol and/or
dimethyl ether in an economical, commercially feasible process.
A further object of the present invention is the provision of a
catalyst, whereby methanol and/or dimethyl ether is converted to a
hydrocarbon product rich in iso-C.sub.4 compounds.
Another important object of the present invention is a method for
producing isobutene in high yield from methanol and/or dimethyl
ether.
These and other objects of the invention are achieved by a process
of contacting a hydrocarbon feed containing methanol and/or
dimethyl ether with a crystalline silica catalyst at elevated
temperature.
It has been discovered that methanol and/or dimethyl ether is
converted to a hydrocarbon product rich in iso-C.sub.4 compounds by
contacting methanol and/or dimethyl ether with a catalyst comprised
of crystalline silica which has a uniform pore structure and
exhibits molecular sieve properties, at a temperature of about
300.degree. to 550.degree. C.
It has further been discovered that a particularly high yield of
iso-C.sub.4 compounds is obtained by contacting methanol, dimethyl
ether or a mixture thereof at a temperature of about 300.degree. to
550.degree. C. with a catalyst having molecular sieve properties
which has been impregnated with one or more metal oxides selected
from thorium oxide, zirconium oxide and titanium oxide.
DESCRIPTION OF THE INVENTION
The conversion of methanol and/or dimethyl ether to a hydrocarbon
product rich in iso-C.sub.4 compounds, in accordance with one
embodiment of the invention, is carried out by contacting methanol,
dimethyl ether or a mixture thereof with a catalyst comprised of
crystalline silica which exhibits molecular sieve properties and is
substantially free of alumina, such as silicalite disclosed in U.S.
Pat. No. 4,061,724. It is critical to use a silica catalyst which
is crystalline since amorphous silica is not an effective catalyst
for this reaction. Further, a pore size of about 5 to 10 .ANG.,
more preferably 5-8 .ANG., and most preferably 5.2 to 6.5 .ANG. and
a uniform pore size are believed to contribute to the effectiveness
of the catalyst in this reaction.
In another embodiment of the invention, methanol and/or dimethyl
ether is converted to a hydrocarbon product rich in iso-C.sub.4
compounds by contact with a catalyst comprised of a crystalline
solid exhibiting molecular sieve properties which has been
impregnated with an oxide selected from thorium, zirconium, or
titanium oxide or a combination thereof. The molecular sieve is
comprised of silica and is preferably a crystalline silica or
crystalline aluminosilicate of uniform pore diameter. It is also
preferable that the catalyst be comprised of crystalline silica
having a pore diameter of about 5 to 10 .ANG., more preferably 5.1
to 8 .ANG., and most preferably a pore diameter of about 5.2 to 6.5
.ANG., such as silicalite impregnated with thorium oxide, zirconium
oxide and/or titanium oxide. A catalyst which has been impregnated
with thorium oxide is particularly preferred.
While catalysts containing up to about 50 parts by weight of oxide
may be used, a preferred catalyst of the invention contains from
about 0.5 to 30 parts by weight of oxide, and a more preferred
catalyst, about 2 to 15 parts by weight of the oxide.
The oxide-containing catalyst may be prepared by any convenient
procedure. For example, the crystalline molecular sieve composition
may be combined with an aqueous solution of a water soluble salt of
the desired metal oxide. After the resultant slurry is dried, the
catalytic composition is packed in a reactor and calcined at a
temperature which does not destroy the crystal structure of the
catalyst, in the range of about 340.degree.-600.degree. C.
Thereafter, the catalyst may be cooled and maintained in an inert
atmosphere, such as nitrogen, until the temperature is that desired
for the reaction.
To produce a hydrocarbon product rich in iso-C.sub.4 compounds in
accordance with the invention, methanol and/or dimethyl ether, or a
mixture thereof, is fed to the reactor into contact with the
catalyst. Water may also be fed to the reactor with the methanol
and/or dimethyl ether, in an amount up to about 80% by weight of
the feed, preferably up to about 70% by weight of the feed.
The temperature of the reactor during the conversion is preferably
within the range of about 310.degree.-550.degree. C., more
preferably about 330.degree. to 455.degree. C. and most preferably,
about 370.degree. to 430.degree. C.
The conversion of methanol and/or dimethyl ether may be carried out
at a pressure of about 0.1 to 20 atms., more preferably about 1 to
10 and most preferably 1 to 4 atms. However, while the conversion
may be carried out at elevated or reduced pressure, it is a
particularly advantageous feature of the process of the invention,
that the conversion may be carried out at ordinary atmospheric
pressure, so that the expense of high pressure equipment may be
avoided.
Methanol, a mixture of methanol and water, dimethyl ether, a
mixture of dimethyl ether and methanol, or a mixture of methanol,
dimethyl ether and water, can be fed to the reactor; preferred
feeds include methanol alone, a mixture of about 90-30% by weight
of methanol and 10-70% by weight of water and an equilibrium
mixture of methanol, dimethyl ether and water. Equilibrium mixture
of methanol, dimethyl ether and water as used herein refers to the
mixture which is obtained when these three components establish an
equilibrium relative to the reaction:
in the temperature range of 250.degree. to 450.degree. C.
Preferably, the mixture is obtained by passing methanol over any
dehydration catalyst, known in the art, one of which is
.gamma.-alumina, at a temperature of about 250.degree. to
450.degree. C. The equilibrium composition is dependent upon the
initial feed composition and the reaction temperature. Therefore,
mixtures of: methanol; dimethyl ether and water; methanol and
water; or dimethyl ether and water can be converted to an
equilibrium mixture at 250.degree. to 450.degree. C. and used as
feed to the catalyst described herein. Most economically, crude
methanol, containing about 80 to 90% of methanol, with the
remainder water, i.e., 10-20% water with minor impurities is
used.
The conversion is desirably carried out at a space velocity varying
from about 0.1 to 20 WHSV, preferably 0.5 to 10 WHSV and most
preferably 0.7 to 5 WHSV.
Ethylene and/or propylene can be recycled to increase the yield of
iso-C.sub.4 compounds.
In another embodiment of the invention, methanol is converted to a
hydrocarbon product rich in iso-C.sub.4 compounds in two or three
stages. In such a process, a dehydrating catalyst such as
.gamma.-alumina is packed near the entrance of the reactor and the
iso-C.sub.4 producing catalyst, i.e., a silicalite,
silicalite-oxide, or other molecular sieve-oxide catalyst, is
packed below the alumina. Methanol is then fed to the reactor,
which is converted by the .gamma.-alumina in the first stage of the
reaction to an equilibrium mixture of dimethyl ether, water and
methanol. In the second stage of the reactor, the equilibrium
mixture is converted to the hydrocarbon product.
A third stage can be added to the reactor to dehydrogenate
isobutane in the hydrocarbon product to the particularly preferred
isobutene.
All types of catalytic reactors usual in the art, including a
fluidized bed, recycle reactor, moving bed reactor, ebulating bed
reactor or a tubular fixed-bed reactor can be used in this
process.
Likewise, other methods may be used to incorporate thorium,
zirconium or titanium oxide in the catalyst and if desired, an
inert carrier or .gamma.-alumina may be present in the
catalyst.
By means of the present process, iso-C.sub.4 compounds are obtained
from methanol, dimethyl ether, a mixture thereof, or a mixture of
any of the foregoing with water, in an amount of 10-50% by weight
of the gaseous products, and more preferably, in the range of 20 to
50% by weight, and most preferably, in an amount of at least 30% by
weight or more.
An advantageous feature of the invention is that the ratio of
isobutylene to isobutane in the product may be maintained in the
range of about 0.6 to 1.0 by feeding water with methanol or
equilibrium mixtures of water, dimethyl ether and methanol to the
reactor.
Another feature of this process is that a high content of
iso-C.sub.4 compounds in the gaseous hydrocarbon product can be
maintained with the concomitant production of either a maximum
amount of aromatic liquid product or a maximum amount of C.sub.2
and C.sub.3 hydrocarbons with a high olefinic content. The
coproduction of liquid aromatics is reduced by cofeeding water with
methanol into contact with the catalyst and by increasing the flow
rate.
The following examples, which were carried out at Texas A&M
University, College of Engineering, College Station, Tex., further
illustrate the best mode currently contemplated for carrying out
the invention, but the invention is not limited in any manner
thereby.
EXAMPLE 1
Preparation of The Catalyst A
Silicalite S-115 from Union Carbide was calcined at 468.degree. C.
for three hours with an air flow rate of 60 cc./min. The calcined
catalyst, numbered A-1 in an amount of 90 cc. (44 g.) was placed in
a tubular reactor 3/4 inch in diameter and approximately 3 feet
long in size, surrounded by an electrical heater and fitted with a
thermocouple.
Conversion of Methanol to Hydrocarbons
Methanol was fed into the reactor packed with catalyst at a rate of
80 cc./hr. (WHSV-1.45 hr..sup.-1) under a pressure of 5.44 atm. The
initial reactor temperature of 396.degree. C. rose to 424.degree.
C. when methanol was introduced. Methanol conversion was 100%; 23.6
wt. % of the (CH.sub.2) group of methanol was converted to organic
liquid, i.e., aromatic hydrocarbons. The distribution of gaseous
product is set forth in Table 1.
EXAMPLE 2
The catalyst used in Example 1 was regenerated by heating with air
at a temperature of 482.degree. C., at an air flow rate of 60
cc./min. After cooling the catalyst to 355.degree. C. with N.sub.2,
methanol was fed into the reactor (WHSV=1.3 hr..sup.-1), whereby
the temperature in the reactor rose to 430.degree. C.
The reaction was continued for 85 minutes to yield a total of 54.3
g. of liquid product, including water and 8.24 g. of liquid
hydrocarbons. The methanol conversion was 100%; 23.2% of (CH.sub.2)
was converted to aromatic hydrocarbons which were principally
alkylated benzenes. The distribution of gaseous product and
parameters of the conversion are set forth in Table 1.
EXAMPLE 3
The catalyst from Example 2 was maintained at 371.degree. C. in a
flow of N.sub.2 (60 cc./min.) overnight and then cooled to
349.degree. C.
When methanol was fed to the reactor the temperature rose to
432.degree. C.; WHSV=1.63 hr..sup.-1.
After 43 minutes, the liquid product collected including
______________________________________ H.sub.2 O was: 58.70 g.
liquid product excluding H.sub.2 O: 15.35 g. CH.sub.3 OH
conversion: 100% DME (dimethyl ether) in product: 0 % (CH.sub.2)
converted to organic liquid: 42.9
______________________________________
The distribution of the product and parameters of the conversion
are shown in Table 1.
EXAMPLE 4
A catalyst used in a preceding example was kept in a current of
N.sub.2 (60 cc./min.) overnight at 331.degree. C. Methanol was fed
into contact with the catalyst in the reactor (WHSV=1.7
hr..sup.-1). The following is the temperature profile during the
conversion:
______________________________________ Time (min) Temp (.degree.C.)
______________________________________ 0 331 7 371 13 378 21 382 29
379 Conversion of CH.sub.3 OH 100% DME 0%
______________________________________
The distribution of the gaseous product and parameters of the
conversion are set forth in Table 1.
EXAMPLE 5
A catalyst from a previous example was cooled to 300.degree. C. in
a flow of N.sub.2 (60 cc./hr.) for 5 hours. Methanol was then fed
to the reactor packed with the catalyst; WHSV=1.7 hr..sup.-1.
The following is the temperature profile during the conversion.
______________________________________ Time (min.) Temp. .degree.C.
______________________________________ 0 300 2 308 13 317 20 322 24
331 26 337 27 339 28 341 29 343 30 345 33 349 38 353 42 358 48 361
56-75 364 Total weight of liquid product 2.8 g. % (CH.sub.2)
conversion to organic liquid 7
______________________________________
The parameters of the conversion and distribution of gaseous
product are set forth in Table 1.
TABLE 1
__________________________________________________________________________
CONVERSION CONDITIONS FLOW Sam- Pres- RATE ple PRODUCT DISTRIBUTION
- WT. % Ex. sure TEMP. CC./ Time trans cis No. Cat. (atm.)
.degree.C. hr. (min.) i-C.sub.4 H.sub.10 n-C.sub.4 H.sub.10
1-C.sub.4 H.sub.8 i-C.sub.4 H.sub.8 2-C.sub.4 H.sub.8 2-C.sub.4
H.sub.8 C.sub.3 H.sub.8
__________________________________________________________________________
1 A-1 5.44 424 80 6 29.0 4.77 1.03 4.37 2.18 1.38 20.57 5.44 424 80
12 31.03 5.30 0.88 3.95 2.05 1.32 22.51 5.44 424 80 23 24.14 4.05
1.34 5.43 2.68 1.73 20.87 5.44 424 80 36 28.16 5.20 1.17 4.52 2.36
1.56 19.98 5.44 424 80 43 25.05 3.97 1.05 4.22 2.01 1.29 19.84 2
A-1 5.44 430 76 85 28.42 3.61 0.61 1.52 1.21 0.76 19.18 3 A-1 5.44
432 90 43 28.89 4.93 1.29 3.08 2.83 1.80 16.77 4 A-1 5.44 378 90 28
29.18 3.95 0.99 2.21 1.76 1.25 14.39 5 A-1 1 317 90 13 27.74 4.40
1.03 3.36 2.11 1.66 11.14 1 345 90 30 17.39 2.20 1.31 2.43 3.06
1.98 6.84 1 364 90 75 20.34 2.33 1.31 3.62 3.07 2.01 7.18
__________________________________________________________________________
CONVERSION CONDITIONS FLOW Sam- Pres- RATE ple Ex. sure TEMP. CC./
Time PRODUCT DISTRIBUTION - WT. % No. Cat. (atm.) .degree.C. hr.
(min.) C.sub.3 H.sub.6 C.sub.2 H.sub.6 C.sub.2 H.sub.4 CH.sub.4 CO
CO.sub.2 H.sub.2
__________________________________________________________________________
1 A-1 5.44 424 80 6 13.60 1.44 13.92 4.85 1.43 1.12 0.34 5.44 424
80 12 10.85 1.64 12.06 5.01 1.68 1.38 0.36 5.44 424 80 23 15.72
1.29 15.64 4.54 1.21 0.96 0.40 5.44 424 80 36 14.22 1.56 13.25 4.55
1.68 1.40 0.39 5.44 424 80 43 15.98 1.67 15.45 5.26 2.10 1.48 0.63
2 A-1 5.44 430 76 85 12.05 1.62 22.67 5.33 1.67 1.19 0.16 3 A-1
5.44 432 90 43 17.93 0.69 13.50 2.79 4.88 0.61 0.02 4 A-1 5.44 378
90 28 13.71 5.23 23.75 2.36 0.66 0.50 0.05 5 A-1 1 317 90 13 15.18
3.52 27.76 1.46 0.00 0.63 0.00 1 345 90 30 35.36 0.21 27.16 1.58
0.04 0.38 0.05 1 364 90 75 34.42 0.58 23.21 1.39 0.01 0.44 0.07
__________________________________________________________________________
EXAMPLE 6
Preparation of catalyst B-1
Ninety mililiters (48.2 g) of silicalite (S-115) from Union Carbide
were heated for 48 hours under vacuum. The thus-treated silicalite
was slowly added to 100 cc. of 0.45M Th(NO.sub.3).sub.4 solution
and mixed. After a period of time to ensure adequate impregnation
of the silicalite, excess Th(NO.sub.3).sub.4 solution was removed
by filtering and the wet Th(NO.sub.3).sub.4 impregnated silicalite
was dried over a water bath and then heated to 180.degree. C. in
vacuum for 72 hours. The catalyst was cooled, packed in the
reactor, and heated to 471.degree. C. for 24 hours under a current
of N.sub.2 to convert Th(NO.sub.3).sub.4 to ThO.sub.2. NO.sub.2
fumes were observed at the outlet of the reactor. The catalyst
charged to the reactor weighed 40.1 g. and occupied a volume of 65
cc. This is catalyst B-1. The maximum possible ThO.sub.2 would be
23% by weight.
The catalyst was cooled in N.sub.2 to a temperature of 313.degree.
C. Methanol was fed to the reactor into contact with the catalyst.
The parameters of the conversion are set forth in Table 3. The
temperature profile of the reaction was as follows:
______________________________________ Time (min.) Temp.
(.degree.C.) ______________________________________ 0 313 3 343 7
377 8 440 13 445 16 (external heating stopped) 452 23 453 30 450 37
447 70 (external heat started) 425 80 (external heat stopped) 431
86 442 100 438 108 432 118 425 122 421 130 415 132 414 136 410 140
408 143 405 172 383 187 368 197 357 200 332 Methanol conversion
100% DME in product 0 % (CH.sub.2) converted to organic liquid 52.6
WHSV = 1.27 hr..sup.-1 ______________________________________
The distribution of gaseous product is shown in Table 2.
EXAMPLE 7
A catalyst prepared as in Example 6 was used except that the
initial temperature in the reactor was 342.degree. C. A mixture of
water and methanol in a 1 to 1 ratio by volume was fed into the
reactor. The parameters of the conversion process and the
distribution of the gaseous products are shown in Table 2. The
temperature profile was as follows:
______________________________________ Time (min.) Temp.
(.degree.C.) ______________________________________ 0 342 4 363 5
367 10 375 11 (heating discontinued) 386 12 391 14 391 20 388 26
388 32 393 % conversion of CH.sub.3 OH 100 % DME 0 % (CH.sub.2)
converted to organic liquid 22.7 WHSV = 1.27 hr..sup.-1 (based on
total feed) WHSVM = 0.54 hr..sup.-1 (based on methanol feed only)
______________________________________
EXAMPLE 8
The same catalyst and methanol-water feed was used as in Example 7
except the initial temperature was 393.degree. C. The conversion
parameters and distributor of gaseous product are shown in Table 2.
The temperature profile was as follows:
______________________________________ Time (min.) Temp.
(.degree.C.) ______________________________________ 0 393 4 416 9
421 28 417 32 423 33 423 35 426 41 429 42 429 45 434 46 433 53 432
56 432 69 433 73 433 % Methanol conversion 100 % DME in product 0 %
(CH.sub.2) converted to organic liquid (aromatics) 10.4 WHSV = 2.4
hr..sup.-1 (based on total feed) WHSVM = 1.0 hr..sup.-1 (based on
methanol feed) ______________________________________
The substantial increase in the production of C.sub.2 and C.sub.3
hydrocarbons, especially C.sub.2 H.sub.4 and C.sub.3 H.sub.6 and
the decreased production of aromatics in Examples 7 and 8 are due
to the addition of water to the feed.
EXAMPLE 9
A catalyst prepared as in Example 6 was maintained at a temperature
of 329.degree. C. in a flow of N.sub.2 ; methanol was then fed to
the reactor under the conditions indicated in Table 2. (The
temperature rose to 458 and then remained steady; samples were
collected at 454.degree. C.) The distribution of the resultant
gaseous product is shown in Table 2.
______________________________________ Liquid products: H.sub.2 O
58.9 g. organic layer 14.6 g. % methanol conversion 100 %
(CH.sub.2) converted to organic 45 liquid DME in product 0 WHSV
1.48 hr..sup.-1 ______________________________________
EXAMPLE 10
A catalyst prepared as in Example 6 was maintained at a temperature
of 378.degree. C. in a current of N.sub.2 ; air was passed through
the catalyst for 1 hour and then the catalyst was cooled to
379.degree. C. Methanol was fed to the reactor and heating was then
discontinued. The parameters of the process and composition of the
gaseous product are shown in Table 2.
______________________________________ % CH.sub.3 OH conversion 100
DME in product 0 % (CH.sub.2) converted to organic 42.1 liquid WHSV
1.44 hr..sup.-1 ______________________________________
EXAMPLE 11
Preparation of Catalyst B-2
Silicalite in an amount of 23.98 g. (50 cc.) and 18 cc. of a 0.45M
solution of Th(NO.sub.3).sub.4 were mixed to form a thick paste,
which was dried to a powder (26.29 g.) by heating over a water bath
and then in an oven at 160.degree. C. at atmospheric pressure. The
resultant catalyst contained 8.4% by weight ThO.
Conversion of Methanol
Fresh catalyst prepared as above was packed in the reactor and
heated overnight in a current of N.sub.2 at 343.degree. C. Methanol
was then fed to the reactor under a flow rate that was varied
during the run.
The temperature, flow rate and distribution of the gaseous product
are set forth in Table 2.
______________________________________ Total CH.sub.3 OH fed: 51.5
cc.; 40.74 g. Total time of reaction: 90 min. Wt. of liquid
product: 9 g. Organic layer H.sub.2 O 22.72 g. % CH.sub.2 converted
to organic liquid 50.5 WHSV 0.63 hr..sup.-1 for 11 min. and then
increased to 1.1 for remaining time
______________________________________
EXAMPLE 12
Preparation of Catalyst B-3
Silicalite (60 g.) was mixed with thorium nitrate soln. (48 cc.
diluted to 100 cc.) to form a slurry. This was mixed with slight
excess of Na.sub.2 CO.sub.3 soln. (110 cc. of 0.425M soln). Boiling
Na.sub.2 CO.sub.3 soln. was added to the boiling Th(NO.sub.3).sub.4
all at once (copious frothing was observed) while stirring
vigorously. After thorough mixing, the solution was filtered
through Watman #1 filter paper with the aid of a vacuum. The
composition was then washed with 500 ml. of deionized water and
finally was dried over a water bath, to obtain 60.24 g. of
catalyst. One half of this (30.12 g.) was slurried again with 10
cc. of K.sub.2 CO.sub.3 soln. containing 0.0143 g. of K.sub.2
CO.sub.3, dried again over a water bath, and calcined at
343.degree. C. in a muffle furance, in a current of air (100
cc./min.) overnight; % ThO=8.9, % K.sub.2 CO.sub.3
.congruent.0.05.
This catalyst, numbered B-3, was packed in the reactor.
Conversion of Methanol
The catalyst was heated to 354.degree. C. in a current of N.sub.2
(60 cc./min.) and then methanol was fed to the reactor the
temperature rose to 391.degree. C. and remained substantially
constant for the length of the run. The other parameters of the
conversion and composition of the gaseous product are set forth in
Table 2.
______________________________________ Time of run 108 min. %
Conversion of (CH.sub.2) to 42 organic liquid WHSV 0.69
______________________________________
EXAMPLE 13
Catalyst B-3 was used.
A mixture of methanol and water (MeOH: H.sub.2 O, 9:1 by vol.) was
fed to the reactor under the condition set forth in Table 2.
______________________________________ WHSV = 0.74 hr..sup.-1
(based on total feed); 0.65 (based on methanol feed) % Conversion
of CH.sub.3 OH 100 % DME in product 0 % (CH.sub.2) converted to
organic liquid 47.2 ______________________________________
The distribution of the gaseous product is set forth in Table
2.
EXAMPLE 14
Preparation of Catalyst B-4
Silicalite in an amount of 90 cc. (48 g.) was combined with 25 cc.
of Th(NO.sub.3).sub.4 solution which had been diluted to 100 cc.
with water.
Phosphoric acid prepared by dissolving 28.5 g. P.sub.2 O.sub.5 in
108 cc. of H.sub.2 O, and then diluting 15 cc. of this solution to
100 cc. was added to the silicalite-Th(NO.sub.3).sub.4 slurry in
small quantities with constant stirring until no precipitation was
noticed in the supernatant solution. Then a slight excess of the
acid was added (in all about 80 cc.). The solids in the beaker were
separated by centrifuging, and washed three times using about 150
cc. of deionized water. The washings were also separated by
centrifuging. Thorium phosphate content was estimated to be
6.6%.
The wet silicalite-thorium phosphate solid was dried over a boiling
water bath and afterwards in vacuum at 140.degree. C.
Sixty cc. (40 g.) of this catalyst numbered B-4 was packed in the
reactor and calcined at 538.degree. C.
Conversion of Methanol
After cooling the catalyst to 371.degree. C. in a current of
N.sub.2, methanol was fed to the reactor under the conditions set
forth in Table 2 for a period of 69 minutes;
The distribution of gaseous products are also set forth in Table
2.
______________________________________ % (CH.sub.2) converted to
organic liquid 52 % DME in product 0 WHSV 0.6 hr..sup.-1
______________________________________
TABLE 2
__________________________________________________________________________
CONVERSION CONDITIONS FLOW Sam- Pres- RATE ple PRODUCT DISTRIBUTION
- WT. % Ex. sure TEMP. CC./ Time trans cis No. Cat. (atm.)
.degree.C. hr. (min.) i-C.sub.4 H.sub.10 n-C.sub.4 H.sub.10
1-C.sub.4 H.sub.8 i-C.sub.4 H.sub.8 2-C.sub.4 H.sub.8 2-C.sub.4
H.sub.8 C.sub.3 H.sub.8
__________________________________________________________________________
6 B-1 1 400-445 53 76 39.0 7.7 1.26 10.28 2.34 3.75 15.67 7 B-1 1
363-393 47 32 19.53 2.06 2.45 13.30 4.70 3.52 5.52 8 B-1 1 393-433
89 73 15.78 1.99 2.66 13.2 3.25 4.8 5.84 9 B-1 1 454 62 24 33.46
6.39 1.18 7.49 2.01 1.60 18.61 10 B-1 1 468 60 58 32.65 4.93 0.89
5.54 1.55 1.03 20.04 1 468-446 60 98 34.68 4.56 0.84 6.11 1.46 1.02
18.87 1 446-436 60 106 35.15 5.08 0.91 6.71 1.75 1.15 18.29 11 B-2
1 371 20 4 49.29 8.21 1.70 9.06 4.39 2.83 14.02 1 373 20 10 42.56
5.69 1.10 6.05 2.20 1.51 16.20 1 403 36 28 37.36 5.45 1.32 7.50
2.76 1.84 16.03 1 403 36 60 34.89 3.80 0.99 6.06 2.54 1.13 15.95 1
399 36 90 32.90 3.42 1.01 5.75 1.58 1.01 16.03 12 B-3 1 388 26 32
36.46 3.49 1.48 7.55 2.56 1.75 11.13 1 391 26 47 34.04 2.91 1.40
7.16 2.25 1.54 11.15 1 391 26 65 33.81 3.68 1.84 9.08 3.69 2.50
10.14 1 391 26 163 31.48 2.66 1.43 7.42 2.43 1.57 10.20 13 B-3 1
384 27 35 32.95 3.33 1.45 7.71 3.21 2.09 9.09 1 395 27 100 26.57
2.19 1.69 8.60 2.82 1.83 8.53 1 393 27 132 26.44 2.09 1.73 8.37
2.60 1.73 8.16 1 413 27 173 26.61 2.37 1.86 8.99 2.85 1.86 8.75 14
B-4 1 377 30 13 47.13 8.74 0.26 1.79 1.02 0.51 25.11 1 393 30 18
42.90 5.35 0.41 2.31 0.68 0.54 27.11 1 412 30 46 37.42 6.19 0.53
2.92 1.06 0.66 29.96 1 414 30 65 37.33 6.56 0.52 3.10 1.03 0.65
29.74
__________________________________________________________________________
CONVERSION CONDITIONS FLOW Sam- Pres- RATE ple Ex. sure TEMP. CC./
Time PRODUCT DISTRIBUTION - WT. % No. Cat. (atm.) .degree.C. hr.
(min.) C.sub.3 H.sub.6 C.sub.2 H.sub.6 C.sub.2 H.sub.4 CH.sub.4 CO
CO.sub.2 H.sub.2
__________________________________________________________________________
6 B-1 1 400-445 53 76 7.34 0.61 8.26 2.27 0.55 0.31 0.21 7 B-1 1
363-393 47 32 28.55 0.44 13.99 2.08 1.14 2.6 0.12 8 B-1 1 393-433
89 73 34.79 0.26 12.80 2.24 1.53 0.68 0.18 9 B-1 1 454 62 24 11.43
1.05 7.43 6.64 1.50 0.74 0.47 10 B-1 1 468 60 58 11.22 1.65 9.42
8.33 1.94 0.37 0.44 1 468-446 60 98 9.36 1.18 10.01
9.51 1.76 0.42 0.21 1 446-436 60 106 9.60 1.06 10.61 7.56 1.42 0.39
0.31 11 B-2 1 371 20 4 2.12 0.38 4.18 1.90 0.00 1.22 0.68 1 373 20
10 11.34 0.74 7.77 2.36 0.00 1.86 0.63 1 403 36 28 14.62 0.63 8.23
3.38 0.00 0.62 0.24 1 403 36 60 14.80 0.83 11.91 4.95 1.34 0.55
0.27 1 399 36 90 15.31 1.39 14.01 5.58 1.51 0.34 0.17 12 B-3 1 388
26 32 16.89 0.94 11.67 3.39 1.75 0.74 0.18 1 391 26 47 18.85 0.68
12.92 4.45 1.40 0.99 0.25 1 391 26 65 19.45 0.63 9.94 3.54 0.74
0.83 0.13 1 391 26 163 20.65 0.69 14.84 4.73 0.64 1.01 0.26 13 B-3
1 384 27 35 18.80 0.69 10.20 1.74 4.10 3.41 1.22 1 395 27 100 26.11
0.53 15.43 3.46 1.06 1.00 0.19 1 393 27 132 25.96 0.54 16.23 3.54
1.08 1.25 0.28 1 413 27 173 25.26 0.61 14.27 4.00 1.21 1.12 0.25 14
B-4 1 377 30 13 4.12 1.03 2.43 3.10 1.66 2.81 0.30 1 393 30 18 7.23
1.38 5.16 3.57 1.70 1.28 0.38 1 412 30 46 9.07 2.06 5.11 3.07 0.93
0.73 0.27 1 414 30 65 9.11 2.42 5.30 2.73 0.84 0.51 0.16
__________________________________________________________________________
EXAMPLE 15
Preparation of Catalyst
The catalyst was prepared from silicalite in an amount of 25 g. (51
cc.) and 4 g. of Zr(NO.sub.3).sub.2 in the following manner:
Zirconium nitrate was dissolved in 30 cc. of deionized water, and
silicalite was added to form a slurry. After thorough mixing, the
slurry was dried over a boiling water bath to dryness and then
heated in the oven overnight at 140.degree. C.; the catalyst
contained about 8.0% ZrO.
This catalyst numbered C-1 was packed in the reactor and calcined
overnight at 541.degree. C. in a flow of air; NO.sub.2 fumes were
observed at the outlet of the reactor; 54 cc. of catalyst was
packed in the reactor.
Conversion of Methanol
Methanol was fed to the reactor, which had been cooled to
379.degree. C. in a current of N.sub.2, under the conditions set
forth in Table 3; the distribution of gaseous products is also set
forth in Table 3.
______________________________________ % conversion of Methanol 100
% DME in product 0 % (CH.sub.2) conversion to organic 60 liquid
WHSV 0.92 hr..sup.-1 ______________________________________
EXAMPLE 16
The catalyst used in Example 15 was regenerated in a current of air
(60 cc./min.) at 515.degree. C. and then cooled in a current of
N.sub.2 to 353.degree. C.
A methanol-water mixture (1:1 by vol.) was fed to the reactor under
the conditions set forth in Table 3 where the distribution of
gaseous product has also been set forth.
______________________________________ Weight of liquid product
organic liquid 16.46 g. H.sub.2 O 32.17 g. Theoretical yield of
H.sub.2 O: 34.4 g. Theoretical yield of (CH.sub.2): 27.5 g. %
(CH.sub.2) conversion to organic liquid 26.9 % conversion of
methanol 100 % DME in gaseous product 0 WHSV 2.36 (based on total
feed) WHSVM 1.05 hr..sup.-1 (based on methanol)
______________________________________
The increase in the proportion of C.sub.2 and C.sub.3 hydrocarbons
especially C.sub.2 H.sub.4 and C.sub.3 H.sub.6 and the decrease in
the proportion of aromatics in the product of Example 16, compared
to the composition of the product of Example 15, are due largely to
the presence of water in the feed.
TABLE 3
__________________________________________________________________________
CONVERSION CONDITIONS FLOW Sam- Pres- RATE ple PRODUCT DISTRIBUTION
- WT. % Ex. sure TEMP. CC./ Time trans cis No. Cat. (atm.)
.degree.C. hr. (min.) i-C.sub.4 H.sub.10 n-C.sub.4 H.sub.10
1-C.sub.4 H.sub.8 i-C.sub.4 H.sub.8 2-C.sub.4 H.sub.8 2-C.sub.4
H.sub.8 C.sub.3 H.sub.8
__________________________________________________________________________
15 C-1 1 462 31 4 23.47 6.16 2.12 9.63 439 2.97 14.91 1 416 31 13
29.48 6.24 1.54 6.87 2.80 1.96 18.95 1 419 31 45 29.90 4.48 1.15
5.20 1.59 1.01 20.98 1 400 31 72 33.83 4.43 1.00 5.13 1.28 0.86
21.52 16 C-1 1 393 71 3 28.77 4.07 2.09 10.57 4.79 3.20 8.69 1 411
71 33 19.23 2.40 2.84 14.70 5.80 4.00 5.98 1 399 71 52 19.76 2.17
2.74 13.46 5.36 3.66 5.65 1 401 71 77 19.07 2.04 2.63 13.15 5.00
3.42 5.68
__________________________________________________________________________
CONVERSION CONDITIONS FLOW Sam- Pres- RATE ple Ex. sure TEMP. CC./
Time PRODUCT DISTRIBUTION - WT. % No. Cat. (atm.) .degree.C. hr.
(min.) C.sub.3 H.sub.6 C.sub.2 H.sub.6 C.sub.2 H.sub.4 CH.sub.4 CO
CO.sub.2 H.sub.2
__________________________________________________________________________
15 C-1 1 462 31 4 22.20 1.37 8.85 2.71 0.71 0.00 0.51 1 416 31 13
18.61 1.20 7.71 2.64 0.70 0.77 0.52 1 419 31 45 19.81 1.08 9.60
3.34 0.79 0.57 0.50 1 400 31 72 16.58 1.30 9.27 3.30 0.71 0.34 0.45
16 C-1 1 393 71 3 23.05 0.20 10.26 0.70 0.00 3.48 0.12 1 411 71 33
31.24 0.21 11.99 1.07 0.26 0.20 0.09 1 399 71 52 31.17 0.21 14.24
1.08 0.33 0.10 0.07 1 401 71 77 32.94 0.21 14.14 1.20 0.33 0.10
0.08
__________________________________________________________________________
EXAMPLE 17
Preparation of Catalyst D-1
A few ml. of TiCl.sub.4 were poured directly into 75 cc. of water,
whereby TiCl.sub.4 hydrolyzed forming a white precipitate, probably
of titanium oxychloride. On standing the precipitate dissolved. The
clear solution was then treated with excess NH.sub.4 OH. A thick
white precipitate of the hydroxide which formed was filtered and
washed repeatedly with deionized water until free of Cl, and was
then dissolved in minimum amount of 1:4 dilute HNO.sub.3.
Thirty cc. of the resultant titanium nitrate solution was diluted
with 30 cc. of deionized water and 32 g. (60 cc.) of silicalite was
added; this mixture was heated to dryness over a water bath and
then to 160.degree. C. for 4 hours. NO.sub.2 fumes were observed
during heating.
A silicalite-TiO.sub.2 catalyst containing 7% by weight of
TiO.sub.2 was obtained, which was packed in a reactor and calcined
at 531.degree. C. in air overnight and then cooled in a current of
N.sub.2 to 364.degree. C. This catalyst is numbered D-1.
Conversion of Methanol
Methanol was fed to the reactor under the conditions indicated in
Table 4 for 111 minutes. The distribution of the gaseous product is
also shown in Table 4.
______________________________________ % CH.sub.3 OH conversion 100
% DME 0 % (CH.sub.2) conversion to organic 48.7 liquid WHSV 0.64
hr..sup.-1 for first 75 min. WHSV 1.27 hr..sup.-1 75 min. to 111
min. ______________________________________
EXAMPLE 18
Catalyst D-1 from Example 17 was regenerated by calcination in air
at 535.degree. C. for 6 hours and then cooled to 364.degree. C. in
a current of N.sub.2.
A mixture of methanol and water (1:1 by volume) was fed to the
reactor for 50 minutes under the conditions indicated in Table 4.
The total volume of methanol-water mixture fed the reactor was 122
cc. which contained 48.3 g. of methanol. The reaction was carried
out for 50 min. and 80.25 g. of liquid product was collected
containing 78 g. of H.sub.2 O and 2.25 of organic liquid.
% (CH.sub.2) converted to organic liquid 10.7.
The distribution of the gaseous product is shown in Table 4.
______________________________________ WHSV 3.4 hr..sup.-1 (total
feed) WHSVM 1.41 hr..sup.-1 (based on methanol feed)
______________________________________
The reduced proportion of aromatics and the increase in the
proportion of C.sub.2 H.sub.4 and C.sub.3 H.sub.6 in the product of
Example 18 compared to that of Example 17 are largely the result of
the addition of water to the feed of Example 18.
TABLE 4
__________________________________________________________________________
CONVERSION CONDITIONS FLOW Sam- Pres- RATE ple PRODUCT DISTRIBUTION
- WT. % Ex. sure TEMP. CC./ Time trans cis No. Cat. (atm.)
.degree.C. hr. (min.) i-C.sub.4 H.sub.10 n-C.sub.4 H.sub.10
1-C.sub.4 H.sub.8 i-C.sub.4 H.sub.8 2-C.sub.4 H.sub.8 2-C.sub.4
H.sub.8 C.sub.3 H.sub.8
__________________________________________________________________________
17 D-1 1 389 28 11 43.79 8.41 0.50 2.32 1.16 0.66 20.45 1 412 28 31
40.02 6.81 0.80 4.02 1.61 1.07 22.87 1 419 28 72 39.41 6.34 0.80
4.52 1.60 1.06 23.31 1 478 80 87 41.17 8.13 1.16 7.07 2.57 1.67
18.09 1 449 80 108 35.44 8.39 1.44 8.49 3.26 2.09 18.47 18 D-1 1
460 146 7 24.77 4.13 2.57 12.34 5.40 3.73 9.60 1 449 146 22 18.29
2.84 2.60 12.46 5.07 3.42 8.28 1 443 146 45 13.03 1.39 2.95 11.65
5.22 3.61 4.10 1 424 146 50 24.14 2.62 2.66 12.92 4.81 3.17 8.66
__________________________________________________________________________
CONVERSION CONDITIONS FLOW Sam- Pres- RATE ple Ex. sure TEMP. CC./
Time PRODUCT DISTRIBUTION - WT. % No. Cat. (atm.) .degree.C. hr.
(min.) C.sub.3 H.sub.6 C.sub.2 H.sub.6 C.sub.2 H.sub.4 CH.sub.4 CO
CO.sub.2 H.sub.2
__________________________________________________________________________
17 D-1 1 389 28 11 5.84 1.69 3.81 2.42 6.88 0.52 1.55 1 412 28 31
10.97 1.01 5.17 3.56 0.87 0.84 0.36 1 419 28 72 11.08 1.50 5.72
3.76 0.60 0.00 0.29 1 478 80 87 9.26 1.45 4.89 3.64 0.45 0.20 0.25
1 449 80 108 9.70 1.26 5.94 4.59 0.46 0.31 0.18 18 D-1 1 460 146 7
23.91 0.41 9.90 2.17 0.58 0.40 0.10 1 449 146 22 28.65 0.59 13.69
2.78 0.75 0.43 0.15 1 443 146 45 42.48 0.43 12.85 1.68 0.33 0.21
0.06 1 424 146 50 34.38 0.47 2.41 2.50 0.82 0.30 0.14
__________________________________________________________________________
* * * * *